DE1545187A1 - Synthetic resin mixtures - Google Patents

Description

Patent attorneys

Dr. Olio Lesssnback 15-45787

Dipl.-Ing. Siraclvs
Bielöieid, Herford Strato W

d, Herford Strato

Weyerhaueser Company, Tacoma Building, i'aooma 1, Washington (USA)

Kunatharagemi see

The present invention relates to kunatbarz solutions in a stable composition that hardens when exposed to pressure and heat are capable and flow easily at low pressures. The present invention relates to particular Kunat resin mixtures, in which an iSpoxydhar * alt an epoxy hardener stable is connected, especially an amino-based hardener, wherein aioh results in a leioht curable mixture, which when applied flows well from elevated temperatures and pressure.

üs began to powderförudgeiCunatharMixan duroh simple physical mixing of epoxy resin, amino hardeners or another hardener and various conventional ones Achieve additives KU. These powdery mixtures however, have the disadvantage of undermining and sole formation, by which the. «er of the mixture is considerably reduced. Aussei These purely physical mixtures cannot be effectively compression set because it is difficult to determine which Remove air xu

Ks is also known to make this Kunethars mixture more intimate

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Mix the same components. The bed parts but react slightly to each other when clean

it mixes intimately in the form of a liquid or fast, so that the mixtures, if they have not at least partially reacted, are not stable at room temperature «On the other hand stable mixtures are obtained if the reaction is allowed to run partially and then interrupted, whereby one However, it contains intermediate products that have already polymerized eo far are that their fluidity at any pressure and every temperature is greatly reduced, making the formmassee less desirable properties, especially for deforming large ropes «

Ss is also known that mixtures compress a powder material iu, get below a non susammenballendes material, but this compression requires high pressures, which in turn increases! Temperature · Since the mixture sound JSpoxydharsen and Bpoxydhartern _f special polyamines and Polykarboneäureanhydriden as In 4er invention, under the conditions of increased pressure and temperature, without hardening, one should assume that the high pressures and high temperatures occurring during compression could cause the highly reactive components to react adversely with one another. The discovery is based on the unexpected discovery that short-term use is very high? Prints result in a powdery material without any noticeable _{agglomeration · BA} _, .._,., *,

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Ια the present invention is ata SpexyAhars, aiii Ipoxy hardener (am batten tin Aainoharter) and an accelerator and anti-adhesive, Pttll- and! artetoff grundlioh trooken and then uatar high druok in 1/4 "diaka coarsely · KlStae pressed, whereby dar firuok immediately relaxes again is used to denote a gate-side approach. the in the diaaa way Terdiohtete * Maeee lit τοη groeeer sepssifisoher Diahta, where dia individual components aar mass, dia noon Haeen doesn’t react with one another, sioh trotadaa don’t dismantle. Usually the mixture is in powder form dam Yerdiohtem aia sjesifisohee Oewicht τοη about 0.5 edar less, aaoh the terdiohte 1.5 - 1.7. fiaa Aarart manufactured material even though without through the gate storability as well due to increased volatility, increased temperature and increased »Sruok, especially sohon at aledrlgerea Druoken ala ala normslerweiee for AIa Terformung dar same ohemieohen Misohings required aiad.

In the case of the Brfiaduag kaaa man ata Ipoxydherakomponeate any polyepoxjr * benuttaa, Aaa under abnormal ataasphere sights Conditions almost iet | dlaa becomes 1 «following» norealerweiee fixed ". On beatan, the chosen Poljapex / d • laa BpasjraAquiTalaaa Toa mindeetene 2, a haben uad Ala Ipeiydgruppe can end permanently or aioht eein, but best of all formed from an oil ether group. Oa aa wuneehieaewert is, highly resktlTe Bpaxydharaa au Terwend and aia Xraeugnla su preserved, since it remains dimensionally stable even at high temperatures,

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should Torsugweise polyepoxides with a SpoxydäquiTalena τοη at least 3 »O, which groups a minimum τοη less reactive like s.B. contain secondary hydroxyl groups. These were advised Polyepexyde are eioh suitable for a speedy and extensive

Heat curing through reaction with polyamines, poly fatty acids a

and their anhydrides and the like «Das Bpoxydhars consists

Torsugweise made of carbon, hydrogen, oxygen and

the functional groups are essentially the epoxy * or

Oxirane group

Torsugte polyepexyds with terminal spoxyd groups are soluble in solvents. Polygltyoidäther τοη Phenols with 3 or more hydroxyl groups in the nucleus, whereby the hydroxyl groups in the nucleus react with a large excess of Ipiealorhytrin in the presence of strong alkalis, especially IaOH, in aiyoldäthergruppen Terwandelt, with IaOI intercepts the chlorohydrin function released by the reaction with the spiohloraydrin reagent. Xatraphenols are particularly suitable, sum Boiopiel 1,1, 2,2-Tetrak * ie (hydroxyphemyl) athanf 1,1, 3,3-Tetrakis- (hydrexyphemyl) propani 1,1, 4,4-Tetrakis (hydroxyphenyl) butanι 1 , 1, 5,5-Trfcraki · (hydroxyphenyl) -3-methylpentane) 1,1, 4,4-Xetrakio (hydroxyphenyl) * 2-aetlgrlsmtani 1,1,8,8-fvetrakis (hydroxyphenyl) oct at j 1, 1,1o, lo-fotrakiohydroxylphenyl) dekanj 1,1,3,5-tetrakie (hydroxyphenyl) -2-ohlerpropani 1,1,3 # 3-tetrakie (hydroxyphenyl) -2-nitropropanej 1,1 ₉ 4 »4-tetrakis (hydroxyphenyl) »2,3-dibromobutane 1,1,6,6-Setrakis (hydrexepheayl) hexanol-2} 1,1,2,2 tetrakis (2-hydroxy-5-methylphenyl) ethane {1,1,3, 3 Tetrakis (4> hydrox «y-2, 6 * diter-

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tertiary butylphenyl) propane ι 1,1,6,6-Tetraki "(3-chloro-4" hydroxyplmyl) hexanj and 1,1,4,4-3! etrakie (2-hydroxynaphthyl) butane.

These letraphenols can be converted into the corresponding glycidyl ether can be transformed, e.g. according to US Patent No. 2 806 o16.

Other iäpoxydharae useful for the invention, which at The epoxidized novolak resins are stable at room temperature. Suitable novolak resins are ü.B. chain-shaped thermoplastic phenol-formaldehyde condensates that daduroh can be produced by reacting a phenol such as carbolic acid or creaol with a sub-molar amount of foraaldehyde leaves, e.g. 0.5-0.8, best 0.6-0.7 moles of formaldehyde each iaol phenol. -Ji β se condensates contain numerous phenolic Hydroxyl groups per molecule and can be epoxidized by üeaittion with an excess of ßpichlorhydrin and simultaneous Withdrawal of the HUl by IsTaOH. The result is a Polyglycidaether of the chain-like condensate, the ale epoxidized lovolak is known. is dpoxidized novolak usually solid and has a jupoxy equivalent of more than 5, o.

Normally solid rolyepoxides with non-terminal jipoxide groups are, for example, 3,4 -Bpoac -ö-aetliyl-oyclohexylMethylene- 3 14-epoxy ~ 6-methyl-oyoloh «xanoarboxylate»

Though one is the more common normally solid epoxy harse such as polyglyoid ethers de »bisphenol Ä (of sufficiently high molecular weight to be able to operate at all under normal conditions

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be firm SU) can use, then they become less prevent *

The epoxy hares of the present invention are thereby hardened, the «they bit normally solid Äpexy hardeners let react, preferably a »polyamine or a Polycarboxylic anhydride. JJpoxy curing agents are known to be in the broadest sense of the word, all connections with a - G-Ct group react.

i) the term "polyamine" means without an organic compound, which contains at least 2 amino groups, each of which provides at least 1 active H-atom. While the ratio is clay polyamine sum Bpoxydhar «strong» wipe t / 2 # -3o weight percentage fluctuates, so it is better to use a stoohiometric ratio Use the following formula.

Mol.wt. Of the polyamine ζ Epexy value * number of poly-

amine shares on 1oo

Number of active H * atoms shares Spoiydhar · needed of polyamines.

The term bpozy value is a common term used for reward the Oxiran-Aq.uiTalente per too grams of Spoxydhars.

The polyamine should ideally be a diamond in which each Amino group is a primary laino group. Polyamines, in where the amino groups are attached to an aromatic nucleus are particularly careful. So beroreugte Polyamines are methylenedianiline, a-phenylenedlamine, and m-tolylene diamln. Although primary diamines are not on one substituted core as a hardening agent at the door lying

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can also be used in Di ami η; aubetitmiertea learn to be used.

Although ielya »inhärtung« can be suggested, there can also be solid pelycarbene sutures, especially in fora lhrar anhydrides be used, ■ · !. Barnatalnalura-oaiydride, Saaaeln- ■ hemeanhydride, Ohl * r «ndio-Anhjdrid ate · Bai use Ton Annydridtn «ardan dlaaa Torsucawalaa in Ä ^ ulTalantan Yarhlltmiaaan τοη 0.4-1.0 Anh / Aritgnajppa ja Kpoacjr-öruppt Tarwandat "

Dia Xunathaxiaiaehttnean dlaaar IrfinAunf contains en mtfgllohat auoh BetriebtIiab · Manganese in rttllatoffen, baaondara inorganic fillerβ, dia wanigatana about · alkallaeh aind · A «eeaten aolltan wanlgatana Kunlgatana from a filler an« anlgatoni a «a filler an« anklgatoni a «a filler an" a "kunatoni a« a filler from "anohatingekajoient 4o or noohatingekajrsoient 4o. Bai den frttharan TarfaJiran led daa Torhandanaaain large yuilstoffantelle during daa marriage in lama formation, whereby the terhareung »eeo was accelerated. In addition, the alkaline American filler tends to be there, the stability of the synthetic resin mixture tended to be, YES · production of τοη misoholes »dt behe * filler content level yerharsung and thus atable artifical mixture * lat daa special concern * of this invention. Generally speaking, about 7o-ea aewiohtspratent can be made of filler and / or pigments, a pro "desat"

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which you could hardly have achieved with the older procedures.

The best fillers are potassium carbonate and barium sulphate, ground asbestos and glass powder, titanium dioxide, zirconium dioxide and powdered alum, mica, clay and tallow. Harder filling pots such as ki et el and yuaris powder can also be used; Ho can trot silica flour "its abrasive properties are used. Ojkimal electrical properties are often obtained by combining fillers, for example fine powdered clay or potassium carbonate together with barium sulfate.

Various other admixtures such as E.B. jintihaftetoffe, which promote the release from egg form, or accelerators can still be Eugesetst.

As is customary with Kunntharsgesee, small additions of urite adhesives should be made to prevent the molded piece from sticking to the mold. The speslfischen non-stick agent is of no importance for the invention. ü _f 5-4, o Crewichtsprosent Kaleiumetearat is a typical adhesive in sufficient 'amount *

Also, üubstaneen cure can accelerate the hardening process • ugesetit · Even liquid accelerators can be used in small amount of the dry mixture can be sugesetet, these being absorbed by the dry components

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without changing their trooke properties. Suitable accelerators are K.B. Phenol, Hesorzin, Catechin and Cresol, tertiary amines, alcohols, dibasic acids etc. The Presence and the selection of an accelerator is of two-tier importance.

The various components of the synthetic resin mixture are best ground separately and the individual powders are then mixed together without a bridge, using a suitable mixing device, a ribbon mixer or a double mixer. The substances should only be thoroughly mixed by being loosely mixed up, avoiding any kneading or any other application of force, which would otherwise generate heat when mixing. In short, the powders are mixed together without kneading, so that a loose mixture results that is almost free of already converted plastic mass.

If the mixed powders initially consist of very small particles, the mixing and milling can first be carried out in a hammer mill at high speed, as this combines intensive mixing with the milling process without the mixture heating up too much. Cooled air can be passed through the hammer mill in a strong current in order to cool the mixture and prevent the individual particles from reacting with one another.

Different «conventional presses are suitable for applying a short pressure and then relaxing quickly? BADORiGINAL 909848/1233

orphans running in the opposite direction are particularly suitable. For example, the mixture can be pressed on an Allia-Chalnere Compaotor, which has a rolling margin of about 0. OO5-0, o2o inches and a hydraulic pressure τοη Ιο, οοο je guadratsoll. This press essentially consists of 2 close-fitting steel rollers, between which »an lets the powder run through, so that the pressure is only applied for a very short time. In the best machines, the waist automatically cuts out as soon as the applied pressure becomes too great. In addition, the folds should be diok enough so that the resulting heat can be dissipated quickly, or cooling liquids should be used to prevent a temperature increase on the roll surface. The ability of the rollers to dissipate heat is very important and also limits the thickness of the pressed pieces to about 1/4 inch, this way premature gumming is avoided despite the fact that the intimately mixed components are already heated.

The new rollers produce a belt-shaped material. To prevent resinification, the tape should be so thin that the heat generated is quickly dissipated. upper urons · for the band thickness is 1/8 of an inch.

The pressed tape is then shredded, ideally too the size of a particle that passes through a 1oer 3 sieve and is held back by a foe. Particles that are too small or too big, they can be pressed and crushed again.

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Bit ao crushed particles represent the mixture, which is then reformed.

The invention is demonstrated using the following examples

lpexied novolak (note 1) 34, Mttaylen di aniline 7.6%

Re βο pure 3.4? *

Clay filler 17.6> Barite (BaSO ^ pigment) 35 _t £ 4 Caloium stearate as anti-adhesive agent 2, o #

All of the gate solid components come in finer Partial size for use as it is after grinding in a hammer mill, i.e. bie the particles duroh an O, o16-inch mesh pass through it.

After grinding, everyone becomes a mixed ingredient mixed with the Reeorsin accelerator in the ribbon mixer until the product is a uniformly distributed, easy-flowing one Powder gives «Then the mixture» wipe two parallel atahlwalten with a whale clearance of 0.110 inches pressed through} the Vtaleen have an initial pressure of 5, ooo o11 per square and a working pressure of 15,000 per square inch. The Walsen population is 1o-3o revolutions per minute, you can read the powdered mixture twice «Know the rulers go through, whereby a product is scored

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is because * di · Pore tinea has a thin band. The tape becomes then granulated and sieved in a conventional chopping machine, the particles being selected, passing through a 10-sieve go through it and hold it back through a 40 sieve will. Although in the example below a sweinallges Throughout the process of applying the V «al sen is the invention In no way limited in this respect and one or more Preesrorgänge can be used to the desired Achieve a tight EU "

The finished powder solution forms coarse, irregularly shaped lumps Pieces. These are filled in polyethylene oil and can be kept indefinitely at 40 ° P.

The Kunstharegemisoh of the lying example is at Terformed under pressure at elevated temperature for 5 minutes. The finished format has the following properties ι

1. Flexibility 8.443 # · square «oll

2. Hookwell hardness 11 · M scale

3. Isod-insolation resistance 0 * 35 foot-lbs / in · (impact test

4. Dimensional stability 282 ° I at 264 J square inches

5. Molded throati 0.06ο in./in.

6. Coeffiiient of the linear 3o-6e ^e C -4.75 x 1o ~ ⁵ thermal expansion 6o-9o ^e C -5.8ο χ 1o " ⁵

7. AewiohtsTerlust 2oo ° C in 1oo hours 5,2 & β. Water absorption 25 ⁰ C in 24 ütd. 0.096 * 9. lttlk / aoeter (spatial / volume factor) 2, · 7

1·. Diohte after Yerformum weighs 1.74

11. Tolumen line resistance 7) * I. 1.26 χ 1o ¹⁶ 5 ·> humidity ohm cm

12. Surface conduction resistance 73 * F 6.14 x 1e ^U ohm

humidity

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13. Dielectric constant (60 Hertz) 4.43 14p loss factor $ 0 ^ ertz) 0.1329

15. Force factor (6o Hertz) 0.03o

16. Solder arc resistance (seconds) 12o

17 * Shelf life of the synthetic resin mixture unlimited at 4-O ⁰ P and also at 73 ⁰ P (in these two temperatures there was no significant loss of fluidity after six months of storage).

Example II

Example I is repeated to make a synthetic resin mixture the following composition!

Jup it oxidizes norolak (application 1) 34, often BeBBteinsic anhydride 15, Oj6 P, P * methylene-biB- (IT,] i-dimethyl-2

aniline)

Silica pulTer 47 Qaloiun btearate 2

The product has essentially the same properties as described under Example I, with the exception of the Simtnsiont stability, dit is 130 ° C at 264 Jt square inches.

Atapitl

Example I is repeated to give an artificial harmony the following composition i

1,1,2,2-Tetraki (hydroxyphenyl) ethane 34,24 ^ Metayltn-dianiline T »7ij6

Hesorcin 2

Kieeele acid flour 54, Oaloium starate 2, oo>

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-H-

Same features wi · under X, old Auenahme the Dimeneionsstabilltät that ^26β ο 0 "el 264 per Quadratioll is.

Anmegkun * I

The epoxidized flOTolak Kunatatoff used in games I and II iat an epoxidized, chain-like condensate clay O-Creaol with formaldehyde, because it arises that 0.65 mol of formaldehyde atit 1 Hol Creaol is allowed to react, so as to obtain a chain-like condensate, the sahlreiohe phenolic OH groups contains * these OH groups are epoxidized by reaction with large molar Ubereohusa Clay lüpichlorhydrin In the presence of τοη MaOH, being a Connection of the following structural formula arises ι

■ tr

L. J 1.2 LJ 3.8

wherein R represents chlorohydrin, glycols and polymeric ethers.

The used, epoxidized MoTolak has a Bpexy-AquiTalen « τοη 4.8, a Jgpoxy-lquiTalentgewicht τοη 225 and one Softening point (Purrans) τοη

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Claims (1)

Claim Toe claim ·! 1. Itabile not demolishable Spoxyd-Kunsthars-Jlieihung, dl · we »· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · s properties, and consists of a tightly pressed mass τοη normally solid polyepoxide and a normally solid hardening agent. The said polyepoxide and the hardening ami ttel are in a finely divided state in an intimate Mleohung pressed TOr ₁ whereby they have essentially not yet reacted with one another. 2. The Bpexykunatharemleehung as in claim 1, in which since the hardening agent is a polycarbonic acid anhydride. 3 · Stable, non-demouldable spoxy-synthetic hair mixture, which can be thermoformed and pressurized, improved when molded, and consists of a densely pre-dried mixture of normally solid polyepoxide and a normally solid polyaminal hardening agent. The said polyepoxide and the polyanln are in a finely distributed state in an intimate atmosphere, whereby they have not reacted with each other in the course of the week. 4. The Spoxykunetharimiaohung as under 3, in the dae added polyepoxide a Polyglyeidaether τοη a Bpexy-ÄqulTalent τοη at least 2.0 let. BATH ORIGINAL 90984 8/123 3 5. The Bpoxykunstharemieohung as under 3, in which the said polyamine is an aromatic polyanine with at least is two primary amino groups. 6. Di · epoxy synthetic chemistry as under 3, the least 2o weight per unit of a slightly alkaline filler contains. 7t Di · Epoxykunsthaniaiechung as under 3, in the dl · said Masee up to "u 1/4 inch diok" 3. stable, non-demixable Bpoxyd-Kunathare rental, which is deformable by warning and pressure, improved tile properties when forcing and consists of a dioht pressed mass up to 1/4 inch, which is normally solid polyepoxide of a Spexy equivalents of at least 3.0 and a normally solid aromatic polyamine with at least 2 primary amino groups as Hartunga means for the said Polytpoxyd contains. That Said polyepoxide and the polyamine are very fine ▼ given condition pressed in intimate mixture before, essentially not yet responding to each other. 9 The 2poxyd-hip mixture as under 6, whereby the Polyepsxyd a Polyglyoidatther lines Phenols with min « at least 3 OH groups in the core. 1o. The Ipexy synthetic hair mixture as under 8, where the said polyepoxide is an epoxidized Hovolak resin. BAD ORIOtMAL 909848/1233 11 · The epoxy-Kunatharz-Misdhung as under 8, whereby the says Polyaaln is a primary diamond made of carbon, Hydrogen and nitrogen iat. The primary amino groups are located on an unsubstituted aromatic nucleus 12 · The fipoxy-kunatharsine mixture as under 11, whereby the said polyamine to the group of methylenedianilines, belongs to m-phenylenediamine and m-tolylenediamine. 13. The Üpoxy-Kunstharzmisohung as under 8, where the Mix at least 4o # of a slightly alkaline filler contains. 14. The Bpoxy-Kunatharz-Mixture as under 8, whereby the Mixture has a specific gravity of 1.5 - 1 «7. 15. The Bpoxy-Synthetic Resin-Makung as under 8, whereby said polyepoxide and polyamine in stoohiometrlsohen Quantities need to be present and awar touching on the number of active Η atoms * »4 of the amino groups of the said polyamines and the number of oxirane groups of the said polyepoxeyds. 16. A Yerfahrea for producing a stable and non-separable epoxy-synthetic resin mixture, the heat- and is compression-deformable, and a Polyepexyd as well as a Härtungsniittel contains in an intimate mixture, the im essentially have not yet reacted with each other, kneading forces being avoided during the Mlschprosessee and the 309848/1233 Misohung Bum dense Zuaaiumenpreaaen a * u kuraeh applies pressure is set. The method as in claim 16, wherein the hardening agent is a polyaaine. 1ü. The method as in claim 16, wherein the mismatch a Walaendruok is auegeeetst, where compressed foils are obtained, which are then comminuted further. BATH ORIGINAL 909848/1233